WO2008069274A1

WO2008069274A1 - Organic polymer bearing plural organic ring structures and a chain structute passing through the ring structures, and process for the production thereof

Info

Publication number: WO2008069274A1
Application number: PCT/JP2007/073599
Authority: WO
Inventors: Takayuki Takeuchi; Norihisa Mino; Nobuaki Kambe; Jun Terao
Original assignee: Panasonic Corporation
Priority date: 2006-12-08
Filing date: 2007-12-06
Publication date: 2008-06-12
Also published as: US20100022737A1; US8507629B2; JPWO2008069274A1; JP4377446B2; JP2009108333A

Abstract

A process for the production of an organic polymer bearing plural organic ring structures and a chain structure passing through the ring structures, which comprises the polymerization step of polymerizing a monomer component consisting of at least one monomer free from ionic functional groups releasing metal ions to form an organic polymer bearing organic ring structures arranged in a state restricted in mobility every prescribed constituent unit. The above monomer component contains a monomer (M) which has both an organic ring structure and a chain moiety passing through the organic ring structure.

Description

Organic polymer comprising a plurality of organic cyclic structures and a chain structure penetrating the organic cyclic structure, and a method for producing the same

The present invention relates to an organic polymer having a plurality of organic cyclic structures and a chain structure penetrating the organic cyclic structure, and a method for producing the same.

Background art

Light

An organic molecule composed of an organic cyclic structure and a chain structure penetrating the organic cyclic structure can have an independent function in the organic cyclic structure and the chain structure. Book

As such an organic molecule, polyrotaxane having a plurality of oral taxane structures in one molecule is known. Polymouth taxanes are expected to have a wide range of applications in fields such as medicine, medicine and electronics.

[0003] As a method for synthesizing a poly (oral) taxane, a method utilizing the hydrophobicity inside the cyclic structure of cyclodextrin and the hydrophilicity outside is known. In an example of this method, cyclodextrin and a chain organic molecule having low water solubility are mixed in an aqueous solvent. In addition, a method of end-capping by modifying or replacing both ends of the guest molecule with a bulky molecule so that cyclodextrin does not fall off is known (A. Harada, J. Li, M. Kam achi). Nature, 356, 325, 1992). Note that the polycapped taxane that is not end-capped may be referred to as a pseudopolyrotaxane.

[0004] In the synthesis method as described above, it is difficult to control the amount of cyclodextrin forming the oral taxane structure. For this reason, as the amount of cyclodextrin increases, the solubility of the polymer decreases due to the hydrogen bonding of the hydroxyl groups of adjacent cyclodextrins, which hinders the progress of the reaction in the solvent. In order to deal with such problems, a method has been proposed in which a hydrophilic monomer and a hydrophobic monomer encapsulated in cyclodextrin are alternately polymerized using a Suzuki copolymerization reaction. (Harry and Anderson, et a

39, 3456-3460, 2000). [0005] All the synthesis methods described above are reactions carried out in an aqueous solvent using cyclodextrin. On the other hand, a method of synthesizing a pseudopolyrotaxane in an organic solvent using permethylcyclodextrin in which the hydroxyl group of cyclodextrin is substituted with a methoxy group has been proposed (M. Okada, M. amachi, A. Harada, Macro Molecule). (Macromolecules, 32, 72 02, 1999). In addition, a method for synthesizing a poly (oral) taxane by a solid phase reaction by mixing an end cap agent and a pseudopolyrotaxane under pressure has been proposed (Japanese Patent Laid-Open No. 2005-75979).

[0006] However, in the method for synthesizing polypolytaxanes described in the aforementioned Harada et al., Okada et al. And JP-A-2005-75979, cyclodextrin or permethylcyclohexane is added to a chain polymer synthesized in advance. Since the dextrin is included, there is a problem that the amount of inclusion cannot be controlled. Furthermore, molecules that can be included as guest molecules by the method of Okada et al. Are limited to molecules such as polypropylene glycol and polytetrahydrofuran disclosed in Okada et al. Therefore, a conjugated polymer that can be used as a conductive polymer cannot be used as a guest molecule.

[0007] In addition, since the method of Harada et al. And Anderson et al. Using cyclodextrin is carried out in an aqueous solvent, in this method, the hydroxyl group of cyclodextrin, which is a hydrophilic functional group, or the ionic functional group of the main chain is used. Water molecules are attracted and water is mixed into the reaction product at the molecular level. Since it is difficult to eliminate the water molecules, the poly (taxane) taxane synthesized by this method has been difficult to use for applications in which water and ions are adversely affected, for example, applications in the electronics field. As a method for solving this problem, a method of replacing the hydrophilic functional group of the synthesized poly (taxane) taxane with a hydrophobic functional group is conceivable. However, the method of replacing all hydrophilic functional groups in the polymer state with hydrophobic functional groups is not practical because of poor reaction efficiency.

Disclosure of the invention

[0008] In consideration of such a situation, the present invention provides an organic polymer having a plurality of organic cyclic structures and a chain structure penetrating the organic cyclic structure, which can be expected to have high properties. This is one of the purposes. Another object of the present invention is to provide a method for producing such an organic polymer. In order to achieve the above object, a first organic polymer of the present invention is an organic polymer comprising a plurality of organic cyclic structures and a chain structure penetrating the plurality of organic cyclic structures, The organic polymer is composed of at least one structural unit, the at least one structural unit does not contain an ionic functional group that releases a metal ion, and the organic cyclic structure does not move. In a limited state, each of the at least one structural unit is arranged for each predetermined structural unit.

In this specification, “polymer” includes a polymer (for example, oligomer) having a low degree of polymerization. In this specification, “polymer” can be read as an organic molecule or a macromolecule.

[0011] Further, the second organic polymer of the present invention is an organic polymer comprising a plurality of organic cyclic structures and a chain structure penetrating the plurality of organic cyclic structures, wherein the chain structure is It is composed of at least one type of structural unit, and the organic cyclic structure is arranged for each predetermined structural unit of the at least one structural unit of the chain structure with limited movement. The chain structure includes a force composed only of the main chain, or the chain structure includes all the functions bonded to the main chain including the main chain and a functional group bonded to the main chain. The group is hydrophobic.

[0012] The first production method of the present invention is a method for producing an organic polymer comprising a plurality of organic cyclic structures and a chain structure penetrating the plurality of organic cyclic structures, wherein metal ions are produced. Polymerization that forms the organic polymer in which the organic cyclic structure is arranged for each predetermined structural unit in a state where movement is restricted by polymerizing at least one monomer that does not contain the ionic functional group to be released. Process. The at least one monomer includes a monomer (M) containing the organic cyclic structure and a chain portion penetrating the organic cyclic structure.

[0013] The second production method of the present invention is a method for producing an organic polymer comprising a plurality of organic cyclic structures and a chain structure penetrating the plurality of organic cyclic structures, wherein the organic cyclic structure A monomer forming step for forming a monomer (M) including a structure and a chain portion penetrating the organic cyclic structure, and polymerizing at least one monomer including the monomer (M) in a non-aqueous solvent. The organic cyclic structure for each predetermined structural unit in a state where movement is restricted A polymerization step of forming the organic polymer in which is disposed. The monomer formation step includes (A) a step of replacing a hydroxyl group bonded to the organic cyclic structure with a hydrophobic group, and (B) the organic cyclic structure so that the chain portion can penetrate the organic cyclic structure. And a step of chemically bonding the chain portion. The step (B) is performed before the step (A), simultaneously with the step (A), or after the step (A).

[0014] In the organic polymer of the present invention, a cyclic structure is regularly arranged for each constant repeating unit of the structural units of the chain structure. Therefore, according to the present invention, an organic polymer having stable performance with little variation in characteristics can be realized. In addition, the first organic polymer of the present invention does not have an ionic functional group that releases a metal ion in the main part of the main chain, and therefore can be easily hydrophobized at the monomer stage. In addition, since the second organic polymer of the present invention has no hydrophilic group bonded to the main chain, it can be synthesized by polymerizing the monomer in a non-aqueous solvent. By synthesizing in a non-aqueous solvent, water contamination at the molecular level can be eliminated. Therefore, according to the present invention, it is possible to obtain a highly reliable organic polymer even in applications where the adverse effects of water and ions are concerned.

Brief Description of Drawings

FIG. 1A and FIG. 1B are diagrams showing examples of the inclusion phenomenon of monomers used in the production method of the present invention.

FIG. 2 shows the chemical formula of cyclodextrin.

FIG. 3 is a diagram showing an example of the production method of the present invention.

FIG. 4 is a diagram showing a part of an example of a synthesis method for the monomer used in Example 1.

FIG. 5A is a diagram showing a reaction following FIG. 4.

FIG. 5B is a diagram showing an example of a method for synthesizing an organic polymer using the monomer formed by the reaction of FIG. 5A.

FIG. 6A is a diagram showing another reaction following FIG. 4.

FIG. 6B is a diagram showing an example of a method of synthesizing an organic polymer using the monomer formed by the reaction of FIG. 6A.

[FIG. 7] FIG. 7 shows a part of an example of a synthesis method for other monomers used in Example 1. FIG.

FIG. 8 is a diagram showing the reaction following FIG. 7.

FIGS. 9A to 9D are diagrams showing another example of a method for synthesizing monomers used in the production method of the present invention.

FIG. 10A is a diagram showing a part of the monomer synthesis method in Example 2.

FIG. 10B is a diagram showing a reaction following FIG. 10A.

FIG. 11 is a diagram showing a monomer polymerization method in Example 2.

FIG. 12 is a diagram showing the NMR measurement results for the polymer synthesized in Example 2.

FIG. 13 is a diagram showing the measurement results of length and height for the polymer synthesized in Example 2.

[FIG. 14] FIGS. 14A to 14C are diagrams showing another example of a method for synthesizing monomers used in the production method of the present invention.

FIG. 15 is a diagram showing a part of the reaction scheme of Example 3.

FIG. 16 shows a part of the reaction scheme of Example 3.

FIG. 17 is a diagram showing a part of the reaction scheme of Example 3.

BEST MODE FOR CARRYING OUT THE INVENTION

[0016] Embodiments of the present invention will be described below. Note that the present invention is not limited to the description of the following embodiments and examples. In the following description, specific numerical values and specific materials may be exemplified, but other numerical values and other materials may be applied as long as the effects of the present invention are obtained.

[First organic polymer of the present invention]

The first organic polymer of the present invention comprises a plurality of organic cyclic structures and a chain structure penetrating the plurality of organic cyclic structures. The first organic polymer is composed of at least one structural unit. None of the at least one structural unit contains an ionic functional group that releases a metal ion! /.

[0018] If the structural unit force is of a type, the structural unit is repeated to form an organic polymer. When there are multiple types of structural units, these structural units are regularly arranged. Or it repeats irregularly and an organic polymer is comprised.

[0019] An ionic functional group that releases a metal ion is a functional group that releases a metal ion (a cation) in a solvent and becomes an anionic group itself, such as a metal salt of a hydroxyl group or a carboxyl group. And metal salts of sulfonic acid groups. For example, if a metal ion is represented by “M ⁺ ”, the basic metal ion such as —0—M ⁺ — COO—M ⁺ — SO—M ⁺ is released.

Three

It is an ionic functional group.

[0020] The at least one structural unit preferably does not contain an ionic functional group. The ionic functional group is a functional group that ionizes in water. Examples of the ionic functional group include a hydroxyl group, a carboxyl group, an amino group, and a sulfonic acid group.

[0021] The organic cyclic structure is arranged for each predetermined constituent unit of the at least one constituent unit in a state where movement is restricted. For example, when an organic polymer is composed of only one structural unit, an organic cyclic structure is arranged for each structural unit. Further, when the organic polymer is composed of plural kinds of structural units, an organic cyclic structure may be disposed in a specific structural unit among them, or an organic cyclic structure is disposed in all the structural units. Also good. For example, when the organic polymer is composed of alternately arranged first structural unit and second structural unit, the organic cyclic structure may be disposed only in the first structural unit. Okay, an organic ring structure is placed in the first and second structural units.

[0022] When there is only one type of structural unit, or when multiple types of structural units are regularly arranged, the organic cyclic structure is regularly arranged for every certain repeating unit.

[0023] The chain structure is formed by a polymerization reaction. By using a chain structure having functionality, an organic polymer having functionality can be obtained. For example, by using a chain structure having conductivity, an organic polymer having conductivity can be obtained. The organic polymer having conductivity can be applied to various uses such as the electronics field. As the chain structure having conductivity, a 71-electron conjugated chain (71-conjugated chain) is preferable. Specifically, those having a structure in which one or more aromatic rings, aromatic condensed polycycles, CH═CH groups, C≡C single groups and the like are connected may be used. The chain structure having conductivity includes at least one group selected from an aromatic ring, an aromatic condensed polycycle, a CH = CH group, and a C≡C group. A plurality may be formed by being connected in a chain.

[0024] The organic cyclic structure is a cyclic structure through which a chain structure can penetrate. The organic cyclic structure may be, for example, a cyclic structure formed of only carbon, or a cyclic structure formed of at least one element selected from oxygen and nitrogen and carbon. Examples of such an organic cyclic structure include a cyclic structure of cyclodextrin (cyclodextrin skeleton) and a macrocycle cyclic structure (skeleton) described later.

[0025] In the organic polymer of the present invention, the movement of the organic cyclic structure is restricted. Specifically, the organic cyclic structure is restrained from the force S that moves from the structural unit in which it is arranged to the adjacent structural unit. Examples of methods for limiting the movement of the organic ring structure include the following.

[0026] In the first example, the chain structure and the organic cyclic structure are chemically bonded. The chemical bond between the two limits the movement of the organic ring structure.

[0027] In the second example, the chain structure contains a side chain, and movement of the organic cyclic structure is restricted by the side chain. The side chain has the size necessary to limit the movement of the organic ring structure.

[0028] The chain structure of the first organic polymer of the present invention preferably does not contain a hydrophilic functional group. Examples of hydrophilic functional groups include a hydroxyl group, a carboxyl group, and a sulfonic acid group.

[0029] In the first organic polymer of the present invention, the number of hydrophobic functional groups bonded to one organic cyclic structure is the same as the number of hydrophilic functional groups bonded to one organic cyclic structure. More than the number is preferred. In this case, it is preferable that the chain structure does not contain a hydrophilic functional group. Examples of the hydrophobic functional group include a hydrocarbon group such as an alkyl group and a trialkylsilyl group such as a trimethylsilyl group.

[0030] In the first organic polymer of the present invention, all functional groups bonded to the organic cyclic structure may be hydrophobic. In this case, it is preferable that the chain structure does not contain a hydrophilic functional group. For example, the organic cyclic structure may be a cyclodextrin cyclic structure, and all functional groups bonded to the organic cyclic structure may be hydrophobic. Specifically, cyclodexterin in which all hydroxyl groups are substituted with hydrophobic groups (for example, alkoxy groups such as methoxy groups). Can use trin. The organic cyclic structure may contain an ether bond.

[0031] The first organic polymer of the present invention is preferably dissolved in a non-aqueous solvent. A polymer that dissolves in a non-aqueous solvent exhibits hydrophobicity and hardly takes up water molecules. Examples of the non-aqueous solvent include organic solvents such as methanol, methylene chloride, toluene, and chloroform.

[Second organic polymer of the present invention]

The second organic polymer of the present invention comprises a plurality of organic cyclic structures and a chain structure penetrating through the plurality of organic cyclic structures. The second organic polymer is composed of at least one structural unit. Similar to the first organic polymer, the organic cyclic structure is arranged for each predetermined constituent unit among the at least one constituent unit of the chain structure in a state where movement is limited.

[0033] The chain structure of the second organic polymer is one of the following two examples. In the first example, the chain structure is composed only of the main chain. In the second example, the chain structure includes a main chain and a functional group bonded to the main chain, and all the functional groups bonded to the main chain are hydrophobic. That is, a hydrophilic functional group is not bonded to the main chain of the chain structure of the organic polymer. Examples of the hydrophilic functional group include a hydroxyl group, a carboxyl group, and a sulfonic acid group. Examples of the hydrophobic functional group include hydrocarbon groups such as alkyl groups and trialkylsilyl groups such as trimethylsilyl groups.

[0034] The second organic polymer of the present invention is an example of the first organic polymer of the present invention. Since the parts other than the above-mentioned features described for the second organic polymer are the same as those for the first organic polymer, the duplicate description is omitted.

[0035] [First production method of organic polymer]

The first method of the present invention for producing an organic polymer is a method for producing an organic polymer comprising a plurality of organic cyclic structures and a chain structure penetrating the plurality of organic cyclic structures. According to the first production method, the first organic polymer of the present invention is obtained. Note that the description overlapping the description of the first organic polymer of the present invention may be omitted. [0036] In the first production method, at least one monomer that does not contain an ionic functional group that releases metal ions is polymerized to form an organic cyclic structure for each predetermined structural unit in a state where movement is limited. Including a polymerization step to form the disposed organic polymer.

[0037] In another aspect, the production method of the present invention is a method in which at least one monomer dissolved in a non-aqueous solvent is polymerized in the non-aqueous solvent, whereby a predetermined transfer is performed in a state where movement is limited. Includes a polymerization step for forming an organic polymer in which an organic cyclic structure is arranged for each structural unit

[0038] The monomer to be polymerized may be one kind or plural kinds, but these monomers do not contain ionic functional groups that release metal ions. The monomer to be polymerized includes a monomer containing an organic cyclic structure and a chain portion penetrating the organic cyclic structure. Hereinafter, this monomer may be referred to as “monomer (M)”. The monomer to be polymerized may be only the monomer (M)! /, And may include the monomer (M) and other monomers! /.

[0039] In one example, a monomer that does not contain an ionic functional group is used. That is, the at least one monomer may be a monomer that does not contain an ionic functional group. Since “ionic functional groups” and “ionic functional groups that release metal ions” have been described above, the description thereof will be omitted.

[0040] As described above, the chain portion of the monomer (M) includes a portion for suppressing the movement of the organic cyclic structure, such as a side chain, a bulky portion, a bent portion, and a cyclic structure. You may go out. Further, the chain portion and the organic cyclic structure may be chemically bonded. The chain portion of the monomer (M) is a molecular chain that forms the above-described chain structure (for example, a chain structure having conductivity) by being polymerized.

[0041] As the organic cyclic structure, the organic cyclic structure described above is used. For example, the organic cyclic structure may be a cyclic structure of cyclodextrin. In this case, all the functional groups bonded to the organic cyclic structure may be hydrophobic. That is, all the hydroxyl groups of cyclodextrin are replaced with hydrophobic groups!

[0042] In the production method of the present invention, it is preferable to form an organic polymer by polymerizing monomers in a non-aqueous solvent. According to this configuration, water molecules and ions can be prevented from remaining in the polymer. Examples of non-aqueous solvents include organic solvents such as methanol and methylene chloride. A solvent is mentioned. In this case, the monomer (M) is a monomer that dissolves in a non-aqueous solvent.

[0043] The production method of the present invention may include a monomer forming step for forming the monomer (M) before the polymerization step. An example of the monomer formation process is given below.

[0044] In the first example of the monomer formation step, first, the hydroxyl group of cyclodextrin is substituted with a hydrophobic group (step (i)). Next, the substituted cyclodextrin and the chain portion are chemically bonded so that the chain portion can penetrate the substituted cyclodextrin (step (ii)). By choosing appropriate conditions (eg solvent), it is possible for the chain moiety to penetrate the cyclodextrin.

[0045] In the second example of the monomer formation step, first, a chain part (1) is passed through cyclodextrin, and this chain part (1) and the chain part (2) having a side chain are chemically treated. Combine.

[0046] In the third example of the monomer formation step, the organic cyclic structure is a macrocycle cyclic structure. This forming step includes a step of forming a chain portion penetrating the macrocycle by reacting two organic molecules having sites that suppress the macrocycle drop-off from both sides of the macrocycle. Two organic molecules can be reacted via a catalyst. By placing the catalytic metal in the center of the macrocycle, it is possible to form a chain portion that penetrates the macrocycle.

[0047] [Second production method of organic polymer]

The second method of the present invention for producing an organic polymer is a method for producing an organic polymer comprising a plurality of organic cyclic structures and a chain structure penetrating the plurality of organic cyclic structures. Hereinafter, the organic polymer produced by the second production method is referred to as “organic polymer (P2)”. The second production method includes a monomer forming step and a polymerization step.

[0048] In the monomer formation step, a monomer (M) including an organic cyclic structure and a chain portion penetrating the organic cyclic structure is formed. Next, in the polymerization process, at least one monomer containing monomer (M) is polymerized in a non-aqueous solvent, whereby organic cyclic structures are arranged for each predetermined structural unit in a state where movement is restricted. An organic polymer (P2) is formed.

[0049] The monomer forming step includes the following steps (A) and (B). In step (A), the hydroxyl group bonded to the organic cyclic structure is substituted with a hydrophobic group. The organic cyclic structure is, for example, a cyclic structure of cyclodextrin. In step (B), the chain portion has an organic cyclic structure. The organic cyclic structure and the chain portion are chemically bonded so that they can penetrate. Step (B) is performed before step (A), simultaneously with step (A), or after step (A).

[0050] The second production method of the organic polymer is an example of the first production method. Therefore, the explanation overlapping with the explanation relating to the first manufacturing method is omitted.

Hereinafter, embodiments of the present invention will be described with examples.

[0052] [Embodiment 1]

In Embodiment 1, an example of an organic polymer in which a chain structure and an organic cyclic structure are chemically bonded will be described.

[0053] First, as shown in FIGS. 1A and 1B, a molecule containing a chain portion to which a cyclodextrin derivative is bound is prepared. In this molecule, one of —CH 2 OH shown in FIG. 2 is bonded to the chain portion in the form of —CH 2 O 3, and all other OH groups are substituted with OCH groups.

[0054] The chain portion is not limited to the chain portion shown in FIGS. 1A and 1B. Specifically, those having a structure in which one or more aromatic rings, aromatic condensed polycycles, CH═CH groups, C≡C single groups and the like are connected may be used. This molecule also has reactive groups G, G ′, and G ″ that serve as reaction points when overlapping at both ends or extending the chain portion to maintain the inclusion state.

[0055] As shown in FIG. 2, cyclodextrin is a cyclic oligomer of glucose, and the size of the cyclic structure changes depending on the number of dalcoses. Therefore, it is possible to select and use a cyclodextrin having a suitable glucose number in accordance with the size of the hydrophobic monomer to be included. In Fig. 2, when n = 4, it is called α-cyclodextrin, when η = 5, it is called / 3-cyclodextrin, and when η = 6, it is called γ-cyclodextrin. .

[0056] The circular structure of the molecules on the left side of Fig. 1 Α and 1B can move with a considerable degree of freedom in the branch part connected to the chain part. Therefore, by adjusting predetermined conditions (for example, solvent conditions), the chain portion can be included in the ring structure as shown on the right side of FIGS. 1A and 1B. In the state on the right side of Figs. 1A and 1B, it may return to the state on the left side of Figs. For this reason, as shown in the schematic diagrams of Fig. 3 (a) and (c), the chain-like portion is extended, or as shown in the schematic diagram of Fig. It is preferable to bind two molecules in an inclusion state to each other. According to these reactions, the chain portion is stably included and a monomer (M) is obtained.

[0057] The obtained monomer (M) can stably exist in a non-aqueous solvent. By polymerizing the monomer (M), a polymer in which an organic cyclic structure regularly encloses a chain structure for each repeating unit is obtained. Mouth taxanes can be synthesized.

[Example 1]

Hereinafter, an example of the first embodiment will be described. The synthesis scheme of the monomer (M) used in Example 1 is shown in FIGS.

[0059] Monomer 1 is synthesized by the reactions of FIGS. 4 and 5A. Monomer 2 is synthesized by the reactions of FIGS. 4 and 6A. Monomer 3 is synthesized by the reactions of Fig. 7 and Fig. 8.

. In Fig. 4 and Fig. 7, the starting material that constitutes the organic ring structure is that one hydroxyl group of α-cyclodextrin is substituted with a tosyl group (CH 1 -CH 2 -SO 1), and all the other

3 6 4 2

A compound obtained by replacing the hydroxyl group with a methyl group was used.

[0060] In the examples of FIGS. 4, 5A, 6A, 7 and 8, monomers having polymerization reaction points at both ends are ethur groups.

(M) is synthesized. Monomers 1, 2 and 3 are polymerized by Eglinton Coupling using Cu (ii) catalyst in the presence of pyridine in an organic solvent. In this way, the organic polymer of the present invention is synthesized. An example of the polymerization reaction of monomer 1 is shown in FIG. 5B, and an example of the polymerization reaction of monomer 2 is shown in FIG. 6B.

[0061] [Embodiment 2]

In Embodiment 2, an example of an organic polymer in which the chain structure has side chains and the movement of the organic cyclic structure is restricted by the side chains will be described.

First, a hydrophobic monomer shown in FIG. 9A and a cyclodextrin are prepared. They are then reacted in an aqueous solvent. The chain structure (chain part) is not limited to the chain structure shown in FIG. 9A, and the chain structure described in Embodiment 1 can be applied. As described in Embodiment 1, there are reactive groups G at both ends of the chain structure.

[0063] As in the first embodiment, the cyclodextrin having a suitable glucose number can be selected and used according to the size of the hydrophobic monomer to be included. Since the above-mentioned hydrophobic monomers are poorly water-soluble, they are taken into cyclodextrins in an aqueous solvent, Included like 9B.

Next, a molecule having a hydrophilic functional group as a side chain, such as the molecule in FIG. 9C, is reacted at both ends of the molecule in FIG. 9B. The molecule in Figure 9C has a reaction that reacts with the reactive group G. The addition of the molecule in Figure 9C yields the molecule in Figure 9D. Here, the functional group of the molecule that reacts with both ends of the molecule in FIG. 9B is not limited to the carboxyl group, and may be another functional group. Further, the structure of the molecule reacted at both ends of the molecule in FIG. 9B is not limited to the thiophene ring, but may be a pyrrole ring or the like.

[0065] The monomer (M) having an oral taxane structure thus obtained is isolated from an aqueous solvent. Next, the monomer (M) is polymerized in a non-aqueous solvent. In this way, an organic polymer having no ionic functional group that releases metal ions can be obtained. This organic polymer is a polyrotaxane. In this organic polymer, the organic cyclic structure is regularly included according to a certain repeating unit of a chain structure. As the polymerization reaction of the monomer (M), for example, ferro coupling can be used.

[0066] Prior to polymerization, the hydrophilic group (hydroxyl group) of the cyclodextrin and the hydrophilic group (carboxyl group) of the chain portion may be substituted with a hydrophobic group.

[0067] [Example 2]

Hereinafter, an example of Embodiment 2 will be described. An example of a scheme for synthesizing the organic polymer of Embodiment 2 is shown in FIG. 10A, FIG. 10B, and FIG.

[0068] First, two types of organic molecules having a chain structure are synthesized by the reaction shown in FIG. 10A. Next, these two kinds of organic molecules are reacted in a liquid containing cyclodextrin as shown in FIG. 10B to synthesize a monomer (M). Monomer (M) is synthesized by the Suzuki copolymerization reaction of the two molecules synthesized by the reaction of Fig. 10A in a ratio of 2 to 1 in the presence of cyclodextrin and palladium catalyst. At this time, one of the organic molecules reacts in a state of being incorporated into the cyclodextrin. In the monomer (M) in Fig. 10 (B), the movement of cyclodextrin is suppressed by the side chain bonded to the chain structure.

Next, as shown in FIG. 11, the monomer (M) is polymerized in a non-aqueous solvent (specifically, methanol). In this way, the organic polymer of Embodiment 2 is synthesized. [0070] Polymers were produced by the synthesis methods shown in Fig. 10A, Fig. 1OB and Fig. 11, and their characteristics were evaluated. Fig. 12 shows the results of ¹ H-NMR. From the results in FIG. 12, it was shown that the synthesized polymer had the structure of the polymer shown in FIG.

[0071] Further, the length and height of the synthesized polymers were measured with an atomic force microscope. The measurement results are shown in FIG. The average length of the polymer was 27.3 nm. This proved that the average degree of polymerization was about 9. The average height of the polymer was about 0.6 nm. This is almost the same as the diameter of one cyclodextrin molecule.

[0072] [Embodiment 3]

In Embodiment 3, an example of using a macrocycle as an organic cyclic structure will be described.

First, a macro cycle as shown in FIG. 14A is prepared. Macrocycles are not limited to the molecules in Figure 14A. However, the macrocycle preferably forms three or more coordination bonds with the metal incorporated inside the annular structure so that the planarity is maintained. Further, when the metal incorporated inside is Pd, the macrocycle is preferably a soft base that is expected to have a relatively strong interaction with Pd, which is a soft acid. Examples of the soft base include a nitrogen-containing cyclic compound as shown in FIG. 14A. The macrocycle of FIG. 14A is schematically shown as a ring in FIGS. 14B and 14C.

[0074] Pd is coordinated to the macrocycle in an organic solvent. Then, as shown in Fig. 14B, the molecule having iodine as the reaction point ("Ar-1" in the figure) and the molecule having boron compound as the reaction point ("(OR) B-Ar '" in the figure) For example by a Suzuki copolymerization reaction. By this reaction, a monomer having a mouth taxane structure is obtained as shown in FIG. 14C.

[0075] The portion indicated by Ar or Ar 'does not contain a hydrophilic group. In addition, they preferably form a π-electron conjugated chain when Ar and Ar ′ are bonded. The two molecules that react are preferably, for example, those having a structure in which one or more aromatic rings, aromatic condensed polycycles, CH = CH groups, C≡C single groups and the like are connected. Furthermore, the part shown as Ar or Ar ′ may have a side chain, a bulky part, or a part where the chain axis is bent. In addition, the portions formed as Ar and Ar ′ have the same plane formed by each cyclic structure. A plurality of cyclic structures that do not lie on one plane may be provided. According to these structures, the movement of the macro-mouth cycle is restricted, and the mouth taxane structure is maintained after the monomer is polymerized. An example of Ar or Ar ′ has a structure in which a hydrophobic group is bonded to an aromatic ring such as a benzene ring.

[0076] By subjecting the mouth taxane monomer to a polymerization reaction in an organic solvent, a polymouth taxane can be obtained. According to this method, it is possible to synthesize polytaxane taxa in which both the chain structure and the organic cyclic structure do not have a hydrophilic group, and the organic cyclic structure is regularly arranged according to a certain repeating unit. .

[0077] [Example 3]

Hereinafter, as an example of Embodiment 3, an example in which an organic polymer can be implemented will be described. An example of a scheme for synthesizing the organic polymer of Embodiment 3 is shown in FIG.

[0078] By the reaction shown in FIG. 15, a macrocycle having palladium incorporated therein is synthesized. Further, by the reaction shown in FIG. 15, a molecule containing an iodine group as a reaction point and a molecule containing a group containing boron as a reaction point are synthesized. Figure 16 shows the synthesis scheme of the material molecules shown in Fig. 15. Note that “BPin” in FIG. 15 means the following groups.

[0079] [Chemical 1]

[0080] The two types of molecules obtained in the reaction of Fig. 15 are reacted by a Suzuki copolymerization reaction in DMSO (dimethyl sulfoxide) using palladium incorporated into the macrocycle as a catalyst. By this reaction, a mouth taxane is synthesized as shown in FIG. In FIG. 17, the macrocycle synthesized by the reaction of FIG. 15 is schematically shown as a circle.

Next, two types of reaction points are added to the obtained mouth taxane by the reaction shown in FIG. One is an iodine group and the other is a group containing boron. These are polymerized by a Suzuki copolymerization reaction using a Pd catalyst in DMSO as shown in FIG. In this way, a polymouth taxane is synthesized.

As described above, the force described in the example of the method for producing the organic polymer of the present invention Each reaction in the formation process may be performed under other known conditions.

Industrial applicability

The organic polymer of the present invention can be applied as a new material such as a functional material in the fields of medicine, medicine and electronics. In particular, when the chain structure has conductivity, it can be applied to an electronic device.

Claims

The scope of the claims

[1] An organic polymer comprising a plurality of organic cyclic structures and a chain structure penetrating the plurality of organic cyclic structures,

The organic polymer is composed of at least one structural unit, and the at least one structural unit does not contain an ionic functional group that releases a metal ion,

The organic cyclic structure is an organic polymer arranged for each predetermined structural unit of the at least one structural unit in a state where movement is restricted.

[2] The organic polymer according to [1], wherein the at least one structural unit does not contain an ionic functional group.

[3] The organic polymer according to [1], wherein the chain structure and the organic cyclic structure are chemically bonded.

[4] The chain structure contains a side chain,

2. The organic polymer according to claim 1, wherein movement of the organic cyclic structure is restricted by the side chain.

5. The organic polymer according to claim 1, wherein the chain structure does not contain a hydrophilic functional group! /.

[6] The number of hydrophobic functional groups bonded to the organic cyclic structure is larger than the number of hydrophilic functional groups bonded to the organic cyclic structure! /, The organic polymer as described.

7. The organic polymer according to claim 1, wherein all functional groups bonded to the organic cyclic structure are hydrophobic.

[8] The organic cyclic structure is a cyclodextrin cyclic structure,

2. The organic polymer according to claim 1, wherein all functional groups bonded to the organic cyclic structure are hydrophobic.

9. The organic polymer according to claim 1, wherein the chain structure has conductivity.

[10] An organic polymer comprising a plurality of organic cyclic structures and a chain structure penetrating the plurality of organic cyclic structures,

The chain structure is composed of at least one structural unit,

The organic cyclic structure has at least the chain structure with the movement restricted. It is arranged for each predetermined structural unit of one kind of structural unit,

The chain structure is composed of only the main chain, or the chain structure includes a main chain and a functional group bonded to the main chain, and all the functional groups bonded to the main chain are hydrophobic. An organic polymer.

[11] A method for producing an organic polymer comprising a plurality of organic cyclic structures and a chain structure penetrating the plurality of organic cyclic structures,

The organic polymer in which the organic cyclic structure is arranged for each predetermined structural unit in a state where movement is restricted by polymerizing at least one monomer that does not contain an ionic functional group that releases a metal ion. Comprising a polymerization step to form

The method for producing an organic polymer, wherein the at least one monomer includes a monomer (M) containing the organic cyclic structure and a chain portion penetrating the organic cyclic structure.

12. The production method according to claim 11, wherein the at least one monomer does not contain an ionic functional group.

[13] The organic cyclic structure is a cyclodextrin cyclic structure,

12. The production method according to claim 11, wherein all functional groups bonded to the organic cyclic structure are hydrophobic.

14. The production method according to claim 11, wherein the at least one monomer is polymerized in a non-aqueous solvent.

[15] Before the polymerization step, including a monomer forming step of forming the monomer (M),

The monomer forming step includes

(i) substituting the hydroxyl group of cyclodextrin with a hydrophobic group;

The method according to claim 11, further comprising the step of (ii) chemically bonding the substituted cyclodextrin and the chain portion so that the chain portion can penetrate the substituted cyclodextrin. .

[16] including a monomer forming step of forming the monomer (M) before the polymerization step;

The monomer formation step includes a step of forming the chain portion penetrating the macrocycle by reacting two organic molecules having sites that suppress the macrocycle drop-off from both sides of the macrocycle. The manufacturing method of Claim 11 containing.

[17] A method for producing an organic polymer comprising a plurality of organic cyclic structures and a chain structure penetrating the plurality of organic cyclic structures,

A monomer forming step of forming a monomer (M) including the organic cyclic structure and a chain-like portion penetrating the organic cyclic structure;

By polymerizing at least one monomer containing the monomer (M) in a non-aqueous solvent, the organic polymer in which the organic cyclic structure is arranged for each predetermined structural unit in a state where movement is restricted. Polymerization step to form a coalescence,

The monomer forming step includes

(A) a step of binding to the organic cyclic structure! /, Replacing the hydroxyl group with a hydrophobic group;

(B) chemically bonding the organic cyclic structure and the chain portion so that the chain portion can penetrate the organic cyclic structure,

The method for producing an organic polymer, wherein the step (B) is performed before the step (A), simultaneously with the step (A), or after the step (A).

18. The production method according to claim 17, wherein the organic cyclic structure is a cyclic structure of cyclodextrin.